1412
J. R. BAILEY.
methylani1i:ie in the presence of a mixture of oxalic and acetic acids, we ‘obtained p-nitrodimethylaniline (Expt. 30). IVe have also prepared several new compounds, notably one froni diphenylamine, the nature of which it is hoped to elucidate later. I I I . Derivatives (7) Monobasic Aliphatic A c i d s . Formanilide, by direct nitration, gave the j J a r a ~ z i kderivative ~ (Exp. 46), which was also obtained in the presence of sulphuric acid (Exp. 42). Acetanilide, by direct nitration, gave a mixture of ovtlzo- and pu?anztro derivatives (Expt. so). In the presence of sulphuric acid, wetanilroucetanilide was obtained (Expt. 47). The oxalic and trichloracetic acid nitrations both gave paranitro d e v i z ~ a t i w s(Expts. 48, 49). The nitrations of trichloracetanilide, propanilide and stearanilide gave products which have not yet been identified. I V . Derivatives of Monobasic Aromatic Acids. Benzanilide yields a mixture of oriho-, nzefa-, and param‘tro del k a fi7,cs by direct nitration (Expt. 7 2 ) . ITith sulphuric acid, parunitrohenzanilide was obtained (Expt. 67). Acetic acid nitration gave w e f a nitrobenzanilide (Expt. 68). 9 mixture of oxalic and acetic acids gave the paranitro derivative (Expt. 69). None of the nitration products of i?z-broniben~anilide, benzenesulphanilide, o-tolylsulphanilide, phenylacetanilide or picranilide have, as yet, been identified, owing to causes beyond our own control. The work described in this paper w a s carried out a t the Johns Hopkins University during the session 1906-7. MCMASTBR UNIVERSITY, TORONTO, CAS., AUguSt, 1907.
[CONTRIRIJTIOS FHOM THE CHEMICAL
LAEORATORY OF T H E
U S I V E R S I T Y OF
TEx.%?.]
HYDANTOIN TETRAZONES. B Y J. R . B A I L E Y .
Received M a y
25,
1908.
Introduction. I n a paper published in this journal a few years ago, the author described some tetrazones, in which there is the group N = N joined on either side t o an hydantoin gr0up.l To simplify the nomenclature, these substances were regarded as azohydantoins. Here an attempt is made t o further establish the constitution of these compounds by showing the relation of dimethylphenylazohydantoin (I), to dimethylphenylhydantoin (11) and also to aminodimethylphenylhydantoin (111). The analytical data, published in the first article, did not in all cases closely agree with the tetrazone formulae. At that time, these substances were prepared for analysis by precipitation from a chloroform ’ THISJOURNAL, 26, 1006.
1413
HYDANTOIN TETRAZONES.
(CH ) C--N-N
=N-I'-C(
I
i
CH,)
(CH,),C-N
l co co
co co
\/
\/
H
(CH,),C-N-NH,
I co 1 co
I t co co
\/
\/
N-C,H,. N-C,H, N-C,H,, N-C,H,, I. 11. 111. solution with petroleum ether. Since then, acetacetic ester has been found to be solvent admirably adapted t o the purification of all azohydantoins investigated. Azodimethylphenylhydantoin, '' obtained snow-white by precipitation from a chloroform solution," as described in the first paper, proved on analysis to be quite impure, but, on crystallization from acetctcetic ester, the substance on analysis gave results, closely agreeing with the assigned formula. Thus purified, the tetrazone decomposes a t 285' (corr.). Calcu!ated for C,.H,,O,N,,: C, 60.83: H,5 . 0 ; : S, 19,35. S a m p l e from CHCI,,.' Found : C,61.85; H , j . 2 6 ; N , 1 8 . 7 1 -18.90. Sample from acetacetic ester. Found : C,60.90; H,5 . 0 9 : S , 19.34.
Dimethylphenylazohydantoin, on heating with dilute sulphuric acid, gives dimethylphenylhydantoin, the constitution of which was established by analysis and also by synthesis from aminoisobutyronitrile and phenylisocyanate. The reaction is not to be interpreted as a simple hydrolysis of the tetrazone, as might be expected, with the formation of nitrous oxide, according to the equation : (CH,),C ---N-N=N-X-C(CH,), 2 (CH,),C--NH
I I \/
1 1 co co
CO CO
\/
I
+H,O=
1
CO CO
\/
+ N,O.
N--C,H, N-C,H, N-C,H, The amount of hydantoin, that can be isolated, is only about one-half the amount, t h a t such a reaction might yield, and a careful determination of the density of the inert gas obtained showed t h a t nitrogen and not nitrous oxide is evolved. An attempt was made to isolate the other decomposition products, t h a t result from the action of sulphuric acid on the tetrazone, in that the sulphuric acid in the filtrate from the hydantoin was removed as barium sulphate and the solution evaporated. The residue, thus obtained, proved very soluble in water and insoluble in the other common solvents, with the exception of alcohol, and could not be made t o crystallize. The action of sulphuric acid on the hydantoin tetrazones is similar to that observed by Renouf in the case of tetramethyltetrazone :* (CH:,),N, H,O = (CH,)," CH,NH, CH,O N?.
+
I
THISJOCRS.\L,
?
/lo.., 13, 2 1 7 3 .
1026.
+
+
+
1414
J. R. ILIILCY.
E. Fischer also observed a similar decomposition in his investigation of tetraethyltetrazone,' which breaks down into nitrogen, ethylamine, diethylamine, and acetaldehyde, the amounts of each of these substances formed being approximately proportional to its molecular weight. The tetrazones, containing hydantoin conipleues, differ in some respects from the simple alkyl tetrazones. The former are solids, which decompose a t high temperatures, while the latter are liquids, which decompose below I j o o . The hydantoin tetrazones rather resemble the aromatic tetrazones These two classes of tetrazones are neutral co.npounds, M hereas the alkyl tetrazones are especially characterized b y strongly basic properties. A further proof of the constitution of the hydantoin tetrazones was obtained from the synthesis of dimethylphenylazohydantoin by the action of bromine water on aniinotlinieth!.lphenylhydantoin: 2(CH3),C---S--SI-I,
I
'
CO CO
(CH,),C -S --S- S -N-C(CF13), 1
I
1
co co
f4Br
\/
'
\/
CO CO
+ .+HBr.
\I'
r\T-CEH5 N-C, H, N-C,H, The author, in conjunction with Barney Brooks, found that the aminohydantoin, employed here, can best be prepared by the action of sulphuric acid on isobutyric-acid-aminodimethylpheliylhydantoin, (CH,),C---NHN-C(CH,), I
COOH
1
1
CO CO
An attempt t o confirm further the constitution of the tetrazones by molecular weight determination of 1-azo-3-rnethyl-j-dimethylhydantoin in chloroform solution was without avail, owing to the insufficient solubility and high molecular weight of this substance. The preparation of dimethylphenylhydantoin from the tetrazone, as referred to above, may be regarded as the last, step in the proof of the constitution of the reaction products of mustard oils on hydrazo acids.? Like the amino acids, the hydrazo acids react with mustard oils through the hydrogen on the nitrogen in the tr-position to the carboxyl group with the formation of thiohydantoins, e . g., hydrazoisobutyric acid gives with phenyl mustard oil ~-dimethyl-~-phenyl-1-isobutyric-acid-amino-2(CH,),C--NE-I
K-C(
CH,),
1 1 boo11 cs co I
\/
N-CEH5,
.-1m1.C'hein., 199,3 2 1 . TIUSJOURSAL, 26, roo6
HYDANTOIN TETRAZONES.
1415
thiohydantoin, which, through a series of reactions, referred to above, may yield dimethylphenylhydantoin. Experimental Part. Preparation o j Dimeth;ylphe7tylhydantoin from Azodimethylphmylhydantoin.-3.8 grams of I-azo-j-dimethyl-3-phenylhydantoin in 2 0 cc. of concentrated sulphuric acid was heated a t 60' for three hours. On pouring the solution into water, there was a partial precipitation of the hydantoin and a further amount was obtained by extraction of the solution with chloroform. The total yield of hydantoin was 1.75 grams. This yield indicates t h a t only one of the hydantoin groups in the tetrazone goes to hydantoin. To determine the fate of the other half of the molecule, the sulphuric acid in the filtrate was precipitated with barium hydroxide and the solution was then evaporated. The residue proved very soluble in water and insoluble in organic solvents, with the exception of alcohol, and could not be made to crystallize. For analysis, the hydantoin was crystallized from water with the addition of charcoal and then from benzene. Calculated for C,,H,,O,N,: Found :
C, 64.71; H , 5 . 8 8 ; N , 13.72. C, 65.13; H, 5.94; N,13.99.
Boiling alcoholic potassium hydroxide also decomposes the tetrazone with the formation of hydantoin. The substance, obtained in this way, before being purified, has a strong terpene odor. The hydantoin, obtained from the tetrazone by the action of sulphuric acid, as described above, crystallizes in long needles, with a characteristic mother-of -pearl luster and, to the naked eye, these are different from the crystals obtained by the action of alcoholic potash on the tetrazone. Under the microscope, the hydantoin, obtained by the acid treatment, consists of long, narrow prisms with very steep dome-shaped end faces, while the hydantoin, obtained by the action of alcoholic potash, appears in the form of thin, broad prisms with dome-shaped end faces not so steep. The hydantoin, obtained by either method, melts undecomposed a t 171O (corr.). The substance is readily soluble in alcohol, chloroform, and benzene, more difficultly soluble in water, and only sparingly soluble in ether. Preparation of Dimethylphenylhydantoirz from Pherzylisocyamte and Aminoisobutyronitri1e.'-Aminoisobutyronitrile, as obtained in ethereal solution, reacts readily with phenylisocyanate with the generation of considerable heat and the hydantoic-acid-nitrile, C,H,NHCONHC(CH,),CN, separates out. This, without further purification, is saponified by boiling with concentrated hydrochloric acid. From the cold, acid solution the dimethylphenylhydantoin separates out almost pure. The hydantoin, Ber., 37, 1921.
1416
J . R . 13.\II,ES.
prepared in this way, is identicnl Ivitli that ol)tained by the action of alcoholic potash on tile tetr:izoiic.. 1Icteriiii)iczti'oii o j lii(, l k i i , i ' / ~ ,o j t h i s I i i i t.t ( ; t i c I
